CN102754020A

CN102754020A - Liquid crystal aligning agent and liquid crystal display element using same

Info

Publication number: CN102754020A
Application number: CN2010800634628A
Authority: CN
Inventors: 野田尚宏; 小田拓郎; 筒井皇晶
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2009-12-14
Filing date: 2010-12-13
Publication date: 2012-10-24
Anticipated expiration: 2030-12-13
Also published as: JPWO2011074546A1; KR101742838B1; TWI502054B; TW201132745A; KR20120103629A; CN102754020B; JP5751171B2; WO2011074546A1

Abstract

Disclosed is a liquid crystal aligning agent which is capable of providing a liquid crystal alignment film that is resistant to film separation or chipping during a rubbing process, has high voltage holding ratio, and does not easily accumulate electrical charges at the initial stage even when a direct current voltage is applied thereto. Specifically disclosed is a liquid crystal aligning agent that contains at least one kind of polymer selected from among polyamic acids, each of which is obtained by having a diamine component containing a diamine represented by formula (1) react with a tetracarboxylic acid dianhydride component, and polyimides that are obtained by imidizing the polyamic acids. (In the formula, Ar represents an isocyclic aromatic compound or a nitrogen atom-containing heterocyclic aromatic compound, and the hydrogen atom on a carbon atom or nitrogen atom constituting the ring may be substituted.)

Description

Aligning agent for liquid crystal and use the liquid crystal display cells of this treating agent

Technical field

The present invention relates to the used aligning agent for liquid crystal of liquid crystal display cells, liquid crystal orientation film and liquid crystal display cells.

Background technology

At present; Liquid crystal orientation film as liquid crystal display cells; Main to use so-called polyimide be liquid crystal orientation film, and this liquid crystal orientation film is the aligning agent for liquid crystal of principal ingredient through coating with the solution of polyimide precursor such as polyamic acid or soluble polyimide and burns till, then implements friction treatment and obtain.

Liquid crystal orientation film is not only controlled the state of orientation of liquid crystal, and is also influential to the characteristic of liquid crystal display cells.Film when especially reducing friction treatment is peeled off, the problem of loss, and the height that suppresses to be accompanied by liquid crystal display cells becomes more meticulous and the contrast of the liquid crystal display cells that takes place descends or it is increasingly important to reduce the characteristic of ghost phenomena.

Polyimide is in the liquid crystal orientation film; As the ghost that is produced by the DC voltage short liquid crystal orientation film of required time that disappears, known use is except the liquid crystal orientation film (for example with reference to patent documentation 1) of the polyamic acid and the aligning agent for liquid crystal of the tertiary amine that also contains ad hoc structure the polyamic acid that contains imide and use and contain the liquid crystal orientation film (for example with reference to patent documentation 2) etc. of aligning agent for liquid crystal that the specific diamines with pyridine skeleton etc. is used as the soluble polyimide of raw material.

In addition; Polyimide is in the liquid crystal orientation film; As the voltage retention height and by the required short liquid crystal orientation film of time of the ghost disappearance of DC voltage generation; The liquid crystal orientation film of the following aligning agent for liquid crystal of known use: this aligning agent for liquid crystal is except containing polyamic acid or its imide amination polymer etc., and the molecule that is selected from that also contains minute quantity contains 1 acid anhydride's compound and the compound (for example with reference to patent documentation 3) that molecule contains the amino compound of 1 uncle.

The prior art document

Patent documentation

Patent documentation 1: japanese patent laid-open 9-316200 communique

Patent documentation 2: japanese patent laid-open 10-104633 communique

Patent documentation 3: japanese patent laid-open 8-76128 communique

Summary of the invention

Invent technical matters to be solved

The present invention In view of the foregoing; Its objective is provides a kind of aligning agent for liquid crystal, and tolerance with loss is strong, voltage retention is high and the liquid crystal structure cell is applied the liquid crystal orientation film that DC voltage also is difficult for taking place initial electric charge savings even this aligning agent for liquid crystal can obtain the film in when friction peeled off.

The technical scheme that the technical solution problem is adopted

The inventor has carried out conscientiously research; The result finds; Comprise use the specific diamine compound contain new compound as the polyamic acid of two amine components and/or with this polyamic acid imidizate and the aligning agent for liquid crystal of polyimide be very effective for the realization of above-mentioned purpose, thereby accomplished the present invention.That is, the present invention has following main points.

(1) a kind of aligning agent for liquid crystal; It is characterized in that; Contain be selected from polyamic acid and with this polyamic acid imidizate and at least a polymkeric substance of polyimide, said polyamic acid reacts with tetracarboxylic dianhydride's composition through two amine components that make the diamine compound that contains following formula [1] expression and gets;

[changing 1]

In the formula [1], Ar representes the heterocyclic aromatic compound of homoatomic ring aromatics or nitrogen atom, constitutes on the carbon atom of ring or the hydrogen atom on the nitrogen-atoms can be substituted.

(2) aligning agent for liquid crystal of above-mentioned (1) record, wherein, the Ar of formula [1] is the heterocyclic aromatic compound of nitrogen atom of homoatomic ring aromatics or the hexatomic ring of hexatomic ring.

(3) aligning agent for liquid crystal of above-mentioned (1) record, wherein, the Ar of formula [1] is the heterocyclic aromatic compound of pentacyclic nitrogen atom.

(4) aligning agent for liquid crystal of above-mentioned (1) record, wherein, the Ar of formula [1] is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine.

(5) the liquid article aligning agent of above-mentioned (1) record; Wherein, the Ar of formula [1] is

azoles,

diazole, thiazole, thiadiazoles, pyrroles, imidazoles, pyrazoles or triazole.

(6) aligning agent for liquid crystal of above-mentioned (1) record, wherein, the diamine compound of formula [1] expression is any compound of formula [4]～[6] expression, wherein, Ar representes implication same as described above;

[changing 2]

(7) aligning agent for liquid crystal of above-mentioned (1) record, wherein, the diamine compound of formula [1] expression is the compound of formula [2] expression, wherein, Ar representes implication same as described above;

[changing 3]

(8) the liquid article aligning agent of each record in above-mentioned (1)～(7) wherein, as two amine components, comprises the diamine compound of above following formula [3] expression of at least 10 moles of %;

H ₂N-Ar’-R ₁-NH-R ₂ [3]

In the formula [3], Ar ' expression phenylene, naphthylene, R ₁Expression C is 1～5 alkylidene, R ₂Expression C is 1～5 alkyl.

(9) the liquid article aligning agent of each record in above-mentioned (1)～(8), wherein, tetracarboxylic dianhydride's composition comprises the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure.

(10) a kind of liquid article alignment films is characterized in that, the aligning agent for liquid crystal of each record in above-mentioned (1)～(9) is coated burnt till on the electroded substrate and get.

(11) a kind of liquid crystal display cells is characterized in that, has the liquid crystal orientation film of above-mentioned (10) record.

(12) diamine compound of following formula [1] expression;

[changing 4]

In the formula [1], Ar representes the heterocyclic aromatic compound of homoatomic ring aromatics or nitrogen atom, and the carbon atom or the hydrogen atom on the nitrogen-atoms that constitute ring can be replaced by organic group.

(13) amines of above-mentioned (12) record, wherein, the Ar of formula [1] is the heterocyclic aromatic compound of nitrogen atom of homoatomic ring aromatics or the hexatomic ring of hexatomic ring.

(14) diamine compound of above-mentioned (12) record, wherein, the Ar of formula [1] is the heterocyclic aromatic compound of pentacyclic nitrogen atom.

(15) diamine compound of above-mentioned (12) record, wherein, the Ar of formula [1] is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine.

(16) diamine compound of above-mentioned (12) record; Wherein, the Ar of formula [1] is azoles,

diazole, thiazole, thiadiazoles, pyrroles, imidazoles, pyrazoles or triazole.

(17) diamine compound of above-mentioned (12) record, wherein, the diamine compound of formula [1] expression is any compound of formula [4]～[6] expression;

[changing 5]

(18) diamine compound of above-mentioned (12) record, wherein, the diamine compound of formula [1] expression is the compound of formula [2] expression;

[changing 6]

(19) a kind of polyamic acid maybe with this polyamic acid imidizate and polyimide, said polyamic acid gets through two amine components that contain the diamine compound of each record in above-mentioned (12)～(18) are reacted with tetracarboxylic dianhydride's composition.

The effect of invention

Tolerance with loss is strong, voltage retention is high and the liquid crystal structure cell is applied the liquid crystal orientation film that DC voltage also is difficult for taking place initial electric charge savings even aligning agent for liquid crystal of the present invention can obtain the film in when friction peeled off; Through using this liquid crystal orientation film, can make the good liquid crystal panel of characteristic.

In addition, through the present invention, a kind of novel diamine compound can be provided, this diamine compound can be used as as raw material of the polyamic acid of aligning agent for liquid crystal and polyimide etc.

The mode that carries out an invention

Aligning agent for liquid crystal of the present invention be contain be selected from polyamic acid and with this polyamic acid imidizate and the aligning agent for liquid crystal of at least a polymkeric substance of polyimide, said polyamic acid reacts with tetracarboxylic dianhydride's composition through two amine components that make the specific diamine compound that contains following formula [1] expression and gets.This specific diamine compound comprises the new compound that does not have record in the document; Through using this specific diamine compound; Even handle in the necessary friction treatment at liquid crystal aligning; Film in the time of also can reducing friction is peeled off and loss, and the voltage retention of gained liquid crystal orientation film is high, even and the liquid crystal structure cell is applied DC voltage also be difficult for taking place initial electric charge savings.

< diamine compound of formula [1] >

In the following formula [1], Ar is the heterocyclic aromatic compound of homoatomic ring aromatics or nitrogen atom, and this Ar becomes the position of the transfer of participating in electric charge, therefore preferably has the structure of electrical activity, wherein the heterocyclic aromatic compound of preferred nitrogen atom.

Ar does not have qualification especially so long as the heterocyclic aromatic compound of homoatomic ring aromatics or nitrogen atom gets final product, if introduce bulky structure or the big ring of molecular weight, then has the possibility of upsetting liquid crystal aligning property, and it is lower therefore to it is desirable to molecular weight.

Ar constitutes the group of 1 valency; Therefore in this manual, for convenience's sake, be designated as the heterocyclic aromatic compound of homoatomic ring aromatics or nitrogen atom etc. as stated; But because Ar constitutes the group of 1 valency; Therefore if express tightly, when then being the homoatomic ring aromatics, be meant that the hydrogen atom with the homoatomic ring aromatics removes the residue after 1; During for the heterocyclic aromatic compound of nitrogen atom, be meant that the hydrogen atom with the heterocyclic aromatic compound of nitrogen atom removes the residue after 1.When being benzene, pyridine, pyridazine, pyrimidine, pyrazine, triazine,

azoles,

diazole, thiazole, thiadiazoles, pyrroles, imidazoles, pyrazoles or triazole, Ar too, is meant that the hydrogen atom with these compounds removes the residue separately after 1.

The form of the ring of the homoatomic ring aromatics of the Ar in the following formula [1] or the heterocyclic aromatic compound of nitrogen atom does not have special qualification, no matter be that five-membered ring or hexatomic ring can both obtain good characteristic.

The heterocyclic aromatic compound of known pentacyclic homoatomic ring aromatics or nitrogen atom is compared with the homoatomic ring aromatics of hexatomic ring or the heterocyclic aromatic compound of nitrogen atom, and the reactivity of ring itself is higher.Therefore, in the sintering process under the high temperature of when the formation of liquid crystal orientation film, implementing, environment-development is given birth to reaction and is taken place crosslinkedly, therefore considers it is preferred from the angle of wear-resisting wiping property.On the other hand, consider the homoatomic ring aromatics of the hexatomic ring of preferred structure good stability or the heterocyclic aromatic compound of nitrogen atom from the angle of the electrology characteristic of liquid crystal orientation film.

Ar in the formula [1] both can be linked by identical ring as biphenylene, bipyridyl, also can as phenylpyridine, phenyl thiophene, be linked each other by different types of ring.Also can as quinoline, benzimidazole, adopt the condensed ring structure.

As the object lesson of above-mentioned homoatomic ring aromatics, the cyclopentadiene of can giving an example, benzene, Azulene, naphthalene, anthracene, phenanthrene, pyrene, aphthacene, benzopyrene 、 perylene, pentacene, phenol naphthalene alkene (phenalene), indenes, fluorenes, inferior biphenyl etc.

As the object lesson of the heterocyclic aromatic compound of above-mentioned nitrogen atom, the pyrroles that can give an example, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, imidazoles, pyrazoles,

azoles, different

azoles, two

azoles, thiazole, isothiazole, thiadiazoles, triazole, tetrazolium, indoles, indazole, benzimidazole, benzo

azoles, benzisoxa azoles, benzothiazole, benzisothiazole, quinoline, isoquinoline, quinoline, phthalazines, quinazoline, quinoxaline, naphthyridines, pteridine, purine, cumarin, isocoumarin, carbazole, acridine, phenanthroline, thienopyridine, furans and pyridine, indolizine, quinolizine, carboline etc.N-H position in pyrroles, pyrazoles, the imidazoles etc. both can maintain the original state, and alkylation such as also can be methylated.

As the preferred object lesson of Ar, the cyclopentadiene of can giving an example, benzene, Azulene, naphthalene, indenes, fluorenes, inferior biphenyl, pyrroles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, imidazoles, pyrazoles,

azoles, different

azoles,

diazole, thiazole, isothiazole, thiadiazoles, triazole, tetrazolium, indoles, indazole, benzimidazole, benzo azoles, benzisoxa

azoles, benzothiazole, benzisothiazole, quinoline, isoquinoline, quinoline, phthalazines, quinazoline, quinoxaline, naphthyridines, pteridine, purine, cumarin, isocoumarin, carbazole, thienopyridine, furans and pyridine, indolizine, quinolizine, carboline.Preferred especially benzene; Pyridine; Pyridazine; Pyrimidine; Pyrazine; Triazine; The pyrroles; azoles;

diazole; Thiazole; Thiadiazoles; Imidazoles; Pyrazoles or triazole.

Constitute on the carbon atom of the ring in the heterocyclic aromatic compound of above-mentioned homoatomic ring aromatics or nitrogen atom or the hydrogen atom on the nitrogen-atoms can be substituted.Substituent kind and quantity do not have special qualification; The substituting group of the electrophilic property that the substituting group of giving electronics property that methyl, ethyl, alkoxy, methoxyl, ethoxy, amino, dimethylamino equimolecular quantity are less and carboxyl, nitro, cyanic acid equimolecular quantity are less can make the transfer activation of electronics, and is therefore preferred.The substituent position of homoatomic ring aromatics or heterocyclic aromatic compound does not have special qualification, during for nitrogenous heterocyclic aromatic compound, substituent optimum seeking site not with the nitrogen-atoms position adjacent.

On the other hand; Liquid crystal aligning property when processing liquid crystal orientation film and rub resistance or synthetic complexity equal angles consider, preferred non-replacement or the homoatomic ring aromatics that has been replaced by less substituting groups such as methyl and ethyls or the heterocyclic aromatic compound of nitrogen atom.

In the diamines of general formula [1] expression, the substituent position of each on the phenyl ring does not have special qualification.The angle of the orientation of the liquid crystal when processing liquid crystal orientation film is considered, position or contraposition between the position relation of 2 amino is preferred in addition, are considered from the angle of the solvent solubility that improves polyamic acid or polyimide, better be between the position.The position of 2 amino relation be between during the position, that is, be 1, during the structure of 3-diaminobenzene, the position of methylene ester is preferably 4 or 5, considers that from effect that improves amino nucleophilicity and the angle that is easy to synthesize good especially is 5.

As the preferred object lesson of the diamines of general formula [1] expression, the compound of the following formula of can giving an example [2], formula [4], formula [5] or formula [6].

[changing 7]

In the formula, the preferred benzene of Ar, pyridine, pyridazine, pyrimidine, pyrazine, triazine, pyrroles,

azoles,

diazole, thiazole, thiadiazoles, imidazoles, pyrazoles or triazole.

< synthesizing of the diamine compound of formula [1] >

The synthetic method of the diamines of general formula [1] expression does not have special qualification, for example can synthesize through with conventional method nitroreduction being transformed into amino method again behind the dinitro compound of synthetic formula [7] expression.

[changing 8]

The dinitro compound of above-mentioned general formula [7] expression can be as follows synthesizes through the esterification of the dinitro benzylalcohol of correspondence.That is, through making dinitro benzylalcohol and acyl chlorides or acid dianhydride in the presence of alkali such as pyridine or triethylamine, react synthetic.Ar is with corresponding as the Ar in the diamines of the above-mentioned general formula [1] of target.

As dinitro benzylalcohol, can give an example 2,4-dinitro benzylalcohol, 3,5-dinitro benzylalcohol, 2,5-dinitro benzylalcohol etc.

[changing 9]

The method that the dinitro compound reduction of above-mentioned general formula [7] expression is obtained the diamines of general formula [1] expression does not have special qualification; Can be to carry out with the reaction of hydrogen, hydrazine, hydrogen chloride etc. in the equal solvent at ethyl acetate, toluene, tetrahydrofuran, two

alkane, alcohol through using palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminium oxide, platinum sulfide carbon etc. as catalyzer.

< two amine components >

The diamines of following formula [1] expression can be through obtaining polyamic acid with tetracarboxylic dianhydride's reaction.Among the present invention, two amine components that use during synthesizing polyamides acid can only be the diamines of formula [1] expression, also can make itself and the combination more than a kind or 2 kinds that is selected from other diamines.

Diamines through containing formula [1] expression is as two amine components, can improve the polyamic acid of gained and with this polyamic acid imidizate and the dissolubility of polyimide in organic solvent.Also have, also be difficult for taking place initial electric charge savings even the rub resistance of the liquid crystal orientation film that is obtained by the aligning agent for liquid crystal that contains this polyamic acid or polyimide is excellent, voltage retention is high and the liquid crystal structure cell is applied DC voltage.For obtaining such characteristic, the diamines of formula [1] expression is preferably 5～100mol% of the synthetic middle two amine component total amounts of using of polyamic acid, and more preferably 10～80mol% is preferably 20～50mol% especially.

In above-mentioned two amine components, the diamines that uses with the diamines combination of formula [1] expression does not have special qualification.The object lesson of these diamines is as follows.

As the example of alicyclic diamine, can give an example 1,4-DACH, 1,3-DACH, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl amine, IPD etc.

As the example of aromatic diamine, the o-phenylenediamine of can giving an example, m-phenylene diamine, p-phenylenediamine (PPD), 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 3; The 5-diamino-N, N-diaryl aniline, 2,4-diamino-N, N '-diaryl aniline, 1,4-diamido-2-methoxybenzene, 2; 5-diamido-P-xylene, 1,3-diamido-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamido-2,5-dichloro-benzenes, 4; 4 '-diaminostilbene, 2-diphenylethane, 4,4 '-diamido-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3; 3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamido-3,3 '-dimethyl diphenylmethane, 2,2 '-diamido Stilbene, 4; 4 '-diamido Stilbene, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl sulfide, 4,4 '-DADPS, 3; 3 '-DADPS, 4,4 '-diamido benzophenone, 1, two (3-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene, 3 of 4-; Two (4-amino-benzene oxygen) benzoic acid, 4 of 5-, 4 '-two (4-amino-benzene oxygen) bibenzyl, 2, two [(4-amino-benzene oxygen) methyl] propane, 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1; Two (4-aminophenyl) cyclohexanes of 1-, α, α-two (4-aminophenyl)-1,4-diisopropylbenzene (DIPB), 9, two (4-aminophenyl) fluorenes, 2 of 9-, two (3-aminophenyl) HFC-236fas, 2 of 2-; Two (4-aminophenyl) HFC-236fas, 4 of 2-, 4 '-diamino-diphenylamine, 2,4-diamino-diphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1; 5-diaminoanthraquinone-, 1,3-diamido pyrene, 1,6-diamido pyrene, 1,8-diamido pyrene, 2,7-diamino-fluorene, 1; Two (4-aminophenyl) tetramethyl disiloxanes of 3-, biphenylamine, 2,2 '-dimethylbenzidine, 1, two (4-aminophenyl) ethane, 1 of 2-, two (4-aminophenyl) propane, 1 of 3-, two (4-aminophenyl) butane, 1 of 4-; Two (4-aminophenyl) pentanes, 1 of 5-, two (4-aminophenyl) hexanes, 1 of 6-, two (4-aminophenyl) heptane, 1 of 7-, two (4-aminophenyl) octanes, 1 of 8-, two (4-aminophenyl) nonanes, 1 of 9-; Two (4-aminophenyl) decane, 1 of 10-, two (4-amino-benzene oxygen) propane, 1 of 3-, two (4-amino-benzene oxygen) butane, 1 of 4-, two (4-amino-benzene oxygen) pentanes, 1 of 5-, two (4-amino-benzene oxygen) hexanes, 1 of 6-; Two (4-amino-benzene oxygen) heptane, 1 of 7-, two (4-amino-benzene oxygen) octanes, 1 of 8-, two (4-amino-benzene oxygen) nonanes, 1 of 9-, two (4-amino-benzene oxygen) decane, two (4-aminophenyl) the third-1 of 10-, 3-two acid esters, two (4-aminophenyl) fourth-1; 4-two acid esters, two (4-aminophenyl) penta-1,5-two acid esters, two (4-aminophenyl) oneself-1,6-two acid esters, two (4-aminophenyl) heptan-1,7-two acid esters, two (4-aminophenyl) are hot-1,8-two acid esters, two (4-aminophenyl) ninth of the ten Heavenly Stems-1; 9-two acid esters, two (4-aminophenyl) last of the ten Heavenly stems-1,10-two acid esters, 1, two [4-(4-amino-benzene oxygen) phenoxy group] propane, 1 of 3-, two [4-(4-amino-benzene oxygen) phenoxy group] butane, 1 of 4-, two [4-(4-amino-benzene oxygen) phenoxy group] pentanes, 1 of 5-; Two [4-(4-amino-benzene oxygen) phenoxy group] hexanes, 1 of 6-, two [4-(4-amino-benzene oxygen) phenoxy group] heptane, 1 of 7-, two [4-(4-amino-benzene oxygen) phenoxy group] octanes, 1 of 8-, two [4-(4-amino-benzene oxygen) phenoxy group] nonanes, 1 of 9-, two [4-(4-amino-benzene oxygen) phenoxy group] decane of 10-etc.

As the example of heterocyclic diamines, can give an example 2,6-diamino-pyridine, 2,4-diamino-pyridine, 2; 4-diamino-1,3,5-triazines, 2,7-diamido dibenzofurans, 3; 6-diamido carbazole, 2,4-diamido-6-isopropyl-1,3,5-triazines, 2; Two (the 4-aminophenyls)-1,3 of 5-, 4-oxadiazole etc.

As the example of aliphatic diamine, can give an example 1,2-diaminoethanes, 1,3-diaminopropanes, 1,4-diaminobutane, 1; 5-diamido pentane, 1,6-diamino hexane, 1,7-diamido heptane, 1,8-diamido octane, 1,9-diamido nonane, 1; 10-diamino decane, 1,3-diamido-2,2-dimethylpropane, 1,6-diamido-2,5-dimethylhexane, 1; 7-diamido-2,5-dimethyl heptane, 1,7-diamido-4,4-dimethyl heptane, 1,7-diamido-3-methylheptane, 1; 9-diamido-5-methylheptane, 1,12-diamido dodecane, 1,18-diamido octadecane, 1,2-two (the amino propoxyl group of 3-) ethane etc.

As the example of aromatic-aliphatic diamines, the diamines of the formula of can giving an example [3] expression.

H ₂N-Ar’-R ₁-NH-R ₂[3]

Here, the Ar ' in the formula is phenylene or naphthylene, R ₁Be carbon number 1～5, better be 1～3 alkylidene, R ₂Being the alkyl of hydrogen atom or carbon number 1～5, better is hydrogen atom or methyl.

As the object lesson of the diamines of formula [3] expression, the 3-amino-benzylamine of can giving an example, 4-amino-benzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminobenzene ethamine, 4-aminobenzene ethamine, 3-amino-N-Methylphenethylamine, 4-amino-N-Methylphenethylamine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-methylamino propyl group) aniline, 4-(3-methylamino propyl group) aniline, 3-(the amino butyl of 4-) aniline, 4-(the amino butyl of 4-) aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(the amino amyl group of 5-) aniline, 4-(the amino amyl group of 5-) aniline, 3-(5-methylamino amyl group) aniline, 4-(5-methylamino amyl group) aniline, 2-(the amino naphthyl of 6-) methylamine, 3-(the amino naphthyl of 6-) methylamine, 2-(the amino naphthyl of 6-) ethamine, 3-(the amino naphthyl of 6-) ethamine etc.

If with the diamines of formula [3] expression and the diamines and the usefulness of formula [1] expression; Then the polyamic acid of gained or polyimide (is polymkeric substance to call them the in the following text) dissolubility in organic solvent further improves; And the liquid crystal aligning property when using as liquid crystal orientation film is excellent, is preferred therefore.Also have, if with diamines of the tilt angle of following increase liquid crystal (below be also referred to as inclination diamines (チ Le De ジアミ Application)) and usefulness, then can give play to the effect of the tilt angle of further increase liquid crystal.Therefore, in the time will obtaining the tilt angle of identical size, even the consumption of inclination diamines also can obtain big tilt angle less.In addition, also be expected to improve the printing of aligning agent for liquid crystal.

The preferred content of the diamines of formula [3] expression is 10～80mol% of two amine component total amounts, more preferably 20～70mol%.

As the diamines (being also referred to as the inclination diamines) of the tilt angle that can increase liquid crystal, can give an example have chain alkyl, the diamines of substituting group that perfluoroalkyl, aromatic series ring-type group, aliphatics cyclic group or they combine, steroid class skeleton group etc.These diamines can also be used with the diamines of formula [1] expression.

Give an example the below object lesson of inclination diamines, but the present invention is not limited to this.In addition, in the formula of below giving an example [12]～formula [38], j representes 5～20 integer, and k representes 1～20 integer.

[changing 10]

[changing 11]

[changing 13]

[changing 14]

[changing 15]

[changing 16]

In the diamines of above-mentioned formula [12]～formula [38], the liquid crystal aligning property of the diamines of formula [12] is excellent, and is therefore preferred.The diamines of formula [19]～formula [26] is very high because of the presentation capability of tilt angle, thus can be used for suitably OCB (optical compensation curved) liquid crystal with alignment films (OCB uses alignment films), vertical alignment-type liquid crystal with alignment films (VA uses alignment films).

For example, the TN liquid crystal is with in the alignment films (tilt angle is 3～5 °), and the content of the diamines of formula [12] is preferably 10～30mol% of two amine component total amounts; With in the alignment films (tilt angle is 10～90 °), the content of the diamines of formula [19]～formula [26] is preferably 5～40mol% of two amine component total amounts to OCB with alignment films or VA.

If consider the balance of each characteristic such as dissolubility, liquid crystal aligning property, pitch angle, voltage retention, savings electric charge of the polyamic acid that uses in the aligning agent for liquid crystal of the present invention or polyimide; Then for example when two amine components of use formula [1], formula [3] and formula [12] expression; The preferred proportion of each two amine component is 10～50% (formula [1])/20～80% (formula [3])/10～30% (formula [12]) with molar ratio computing, more preferably 20～40% (formula [1])/30～50% (formula [3])/10～30% (formula [12]).

< tetracarboxylic dianhydride's composition >

In necessary polyamic acid of aligning agent for liquid crystal of the present invention or the polyimide, the tetracarboxylic dianhydride's composition that reacts with above-mentioned two amine components does not have special qualification.That is, not only can use a kind of tetracarboxylic dianhydride, also can the tetracarboxylic dianhydride more than 2 kinds also use.

In the aligning agent for liquid crystal of the present invention, consider from the angle of the voltage retention that can further improve the liquid crystal structure cell, as with the tetracarboxylic dianhydride of said two amine components reaction, preferably use tetracarboxylic dianhydride with alicyclic structure or aliphatic structure.

As tetracarboxylic dianhydride, can give an example 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1 with alicyclic structure or aliphatic structure; 3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3; 4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2,4; 5-cyclohexane tetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, [4-(2,5-dioxo tetrahydrofuran-3-yl)-1,2,3; 4-naphthane-1,2-dicarboxylic anhydride], 1,2,3,4-butane tetracarboxylic acid dianhydride, dicyclo [3,3,0] octane-2,4,6; 8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, suitable-3,7-dibutyl ring is hot-1,5-diene-1,2; 5,6-tetracarboxylic dianhydride, three ring [4.2.1.02,5] nonanes-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.12,7.03; 6.19,14.010,13] and hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dianhydride etc.Wherein, if use 1,2,3,4-cyclo-butane tetracarboxylic dianhydride then can obtain the excellent alignment films of liquid crystal aligning property, and is therefore preferred especially.

Also have,, then can improve liquid crystal aligning property, and can accelerate the release of the savings electric charge of liquid crystal structure cell if also use aromatic tetracarboxylic acid's dianhydride.As aromatic tetracarboxylic acid's dianhydride, the pyromellitic acid anhydride, 3 of can giving an example, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3; 3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4; 4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1; 2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.Wherein, preferred especially pyromellitic acid anhydride.

If consider the equilibrium of each characteristic such as orientation, voltage retention, savings electric charge of dissolubility, the liquid crystal of polyamic acid or the polyimide of gained; Have alicyclic structure or aliphatic structure tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride usage ratio with the former/latter's molar ratio computing is preferably 90/10～50/50, better is 80/20～60/40.

< polyreaction >

In the present invention, the polymerisation process to tetracarboxylic dianhydride's composition and two amine components does not have special qualification.Generally can obtain polyamic acid to carry out polyreaction, obtain polyimide through making this polyamic acid dehydration closed-loop through in organic solvent, mixing.

As making tetracarboxylic dianhydride's composition and two amine components method of mixing in organic solvent; The solution that gets making two amine components be dispersed or dissolved in organic solvent of can giving an example stirs, and directly adds tetracarboxylic dianhydride's composition then or makes tetracarboxylic dianhydride's composition be dispersed or dissolved in the method for adding again behind the organic solvent; Add the method for two amine components in the solution that gets making tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent on the contrary; Alternately add the method for tetracarboxylic dianhydride's composition and two amine components etc.In addition, when tetracarboxylic dianhydride's composition or two amine components were made up of multiple compound, the state that said multiple composition can be pre-mixed carried out polyreaction, also can carry out polyreaction respectively successively.

Temperature when tetracarboxylic dianhydride's composition and two amine components carry out polyreaction in organic solvent is generally 0～150 ℃, is preferably 5～100 ℃, better is 10～80 ℃.The high more polyreaction of temperature is accomplished more soon, if but too high then can't obtain high molecular weight polymers sometimes.

In addition, polyreaction concentration is arbitrarily carried out, if the total concentration of tetracarboxylic dianhydride's composition and two amine components is low excessively; Then be difficult to obtain high molecular weight polymers; If excessive concentration, then the viscosity of reactant liquor can become too high, is difficult to even stirring; Therefore total concentration is preferably 1～50 quality %, more preferably 5～30 quality %.Can carry out with high concentration at the polyreaction initial stage, and then append organic solvent.

Employed organic solvent during above-mentioned polyreaction does not have qualification especially so long as the organic solvent of the polyamic acid that dissolving generates get final product.Its object lesson if give an example; N then can give an example; Dinethylformamide, N; N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.These can use separately, also can mix use.Also have, even the insoluble solvent of separating polyamic acid, so long as in the scope that the polyamic acid that generates can not be separated out, also can use with above-mentioned solvent.In addition, the moisture in the organic solvent can hinder polyreaction and then make the polyamic acid hydrolysis of generation, so organic solvent better is to dehydrate the back to use as far as possible.

Tetracarboxylic dianhydride's composition and diamines components in proportions used in the polyreaction of polyamic acid are preferably 1:0.8～1:1.2 with molar ratio computing, and this mol ratio is more near 1:1, and the molecular weight of the polyamic acid of gained is big more.Through controlling the molecular weight of this polyamic acid, can adjust the molecular weight of the polyimide that obtains behind the imidizate.

The molecular weight of polyamic acid of the present invention or polyimide does not have special qualification; But when being contained in aligning agent for liquid crystal; The intensity of filming from gained and consider as the angle of the processing convenience of aligning agent for liquid crystal; Be preferably 2000～200000 in weight-average molecular weight, more preferably 5000～50000.

< synthesizing of polyimide >

Used polyimide is with above-mentioned polyamic acid imidizate and the polyimide that gets in the aligning agent for liquid crystal of the present invention.The imidizate of polyamic acid can be realized through in organic solvent, in the presence of base catalyst and acid anhydrides, stirring in 1～100 hour.

As base catalyst, can give an example pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein preferred pyridine is because it has the suitable alkalescence that the reaction of making is carried out.

As acid anhydrides, can give an example acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc.Wherein preferred acetic anhydride is because after the imidizate end, the polyimide of gained is easy to purifying.

As organic solvent, used solvent in the time of can using above-mentioned polyamic acid polyreaction.

The imidizate rate of polyimide can wait and control through adjusting catalytic amount, temperature of reaction, reaction time.The amount of the base catalyst of this moment is 0.2～10 times of mole of acid amides acidic group preferably, is more preferably 0.5～5 times of mole.The amount of acid anhydrides is 1～30 times of mole of acid amides acidic group preferably, is more preferably 1～10 times of mole.Temperature of reaction better is-20～250 ℃, is more preferably 0～180 ℃.

The imidizate rate of used polyimide does not have special qualification in the aligning agent for liquid crystal of the present invention; In order to obtain the liquid crystal orientation film of higher voltage retention; The imidizate rate is preferably more than 40%, more preferably more than 60%, particularly preferably in more than 80%.

The remaining catalyzer that interpolation is arranged of the solution of the polyimide that obtains like this etc. when therefore being used for aligning agent for liquid crystal, better are to re-use after polyimide is reclaimed, cleans.

Filter after the recovery of polyimide can separate out polyimide through the Weak solvent that the solution input behind the imidizate is being stirred and realize.As the Weak solvent of this moment, can give an example methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.The cleaning of the polyimide after the recovery also can be carried out with this Weak solvent.Carry out normal temperature or heat drying under the polyimide that obtains after reclaiming like this, cleaning can or reduce pressure at normal pressure and form powder.

This operation also can be carried out above-mentioned polyamic acid.For example, when not wanting to make solvent used in the polymerization that contains polyamic acid in the aligning agent for liquid crystal, when perhaps wanting to remove unreacted monomer component and the impurity in the reaction solution, can carry out above-mentioned deposition and reclaim and purifying.

< aligning agent for liquid crystal >

Aligning agent for liquid crystal of the present invention is to contain by the polyamic acid of above-mentioned gained and the coating fluid of at least a polymkeric substance in the polyimide.

It makes example if give an example, and then can directly use the reaction solution of above-mentioned polyamic acid or polyimide, perhaps can after diluting, use, and perhaps also can use after the product that reclaim and get is dissolved in organic solvent once more precipitating from reactant liquor.In addition, dilution and again in the dissolution process can be used for the adjustment of the solvent composition of the coating on the control basal plate, and is used to improve the appending etc. of additive of coating characteristic.Also have, can mix with having, perhaps can add other resinous principle with the solution of the polyimide of above-mentioned various structure or the solution of polyamic acid.

As above-mentioned dilution and the organic solvent that uses in the dissolution process again,, do not have especially and limit so long as the organic solvent of the polymkeric substance that solubilized contains gets final product.As its object lesson; N can give an example; Dinethylformamide, N; N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.Wherein, preferably use N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, 1,3-dimethyl-imidazolinone, gamma-butyrolacton.These can use to mix more than a kind or 2 kinds and use.

As in order to control coating and the solvent that add of aligning agent for liquid crystal on substrate, the ethyl cellosolve of can giving an example, butyl cellosolve, ethyl carbitol, BC, ethyl carbitol acetic acid esters, monoethylene glycol, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, diethylene glycol diethyl ether, propylene glycol monoacetate, propylene-glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetic acid esters, the single ether of propylene glycol-1--2-acetic acid esters, DPG, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.Also comprise the solvent that can not dissolve polyamic acid or polyimide separately in these solvents, but as long as in the scope that polymkeric substance is not separated out, these solvents can be mixed in the aligning agent for liquid crystal of the present invention.Particularly have the solvent of low surface tension, can improve the homogeneity of filming when coating substrate, so this kind solvent also is suitable for aligning agent for liquid crystal of the present invention through suitable mixing.Wherein, consider preferred especially butyl cellosolve, ethyl carbitol, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether from the deliquescent angle of polyimide.

As the additive that is used to improve coating characteristic, silane coupling agents such as the 3-aminopropyl methyldiethoxysilane of can giving an example, 3-phenyl amino propyl trimethoxy silicane, 3-aminopropyltriethoxywerene werene, (aminoethylamino methyl) phenethyl trimethoxy silane.Through adding these silane coupling agents, can improve the adaptation of filming to substrate, but addition aggegation easily such as polyamic acid or polyimide when excessive.Therefore, the content of silane coupling agent is preferably 0.5～10 quality % with respect to the gross mass of polyamic acid or polyimide, more preferably 1～5 quality %.

The solid component concentration of aligning agent for liquid crystal of the present invention can according to the setting of thickness of the liquid crystal orientation film that will form do appropriate change, better be 1～10 quality %.If less than 1 quality % then is difficult to form even and flawless filming, if be higher than 10 quality %, the storage stability variation of solution sometimes then.Here said solid constituent is meant from aligning agent for liquid crystal and removes the composition after desolvating.In addition; The used polyamic acid or the concentration of polyimide do not have special qualification in the aligning agent for liquid crystal of the present invention, but consider from the angle of the characteristic of gained liquid crystal orientation film, preferably more than 1 quality %; More preferably more than 3 quality %, more than 5 quality %.

As above the aligning agent for liquid crystal of gained preferably filtered earlier before coating substrate.

< liquid crystal display cells >

Aligning agent for liquid crystal of the present invention can be through coating substrate, and is dry, burn till the back and form and film, and again through this coated surface is carried out friction treatment, is used as the liquid crystal orientation film of friction usefulness.In addition, the VA that also can be used as without friction treatment uses (vertical orientated usefulness) liquid crystal orientation film, optical alignment film.

At this moment; Used substrate is not so long as the high substrate of the transparency then has special qualification; Can use plastic bases such as glass substrate, acrylic acid substrate or polycarbonate substrate etc., consider, the preferred substrate that is formed with the ITO electrode that is used for liquid crystal drive etc. that uses from the angle that production technology is simplified.In addition, in the reflection type liquid crystal display element, can use opaque materials such as silicon wafer, but only limit to the substrate of a side, the electrode of this moment can use reflectorized materials such as aluminium.

As the coating process of aligning agent for liquid crystal, can give an example spin-coating method, print process, ink-jet method etc., but consider from the productivity aspect, the industrial circle hectographic printing method that is widely used, this method also is suitable for aligning agent for liquid crystal of the present invention.

Drying process after the coating of liquid crystalline aligning agent is also nonessential, but in the time till burn till after the coating every substrate under all unfixed situation or under the situation of not burning till immediately after the coating, is preferably included drying process.Dry so long as make solvent evaporation, reach the shape of filming can be because of the transportation of substrate etc. former thereby degree distortion do not get final product, this drying means is not had special qualification.For example, can give an example on 50～150 ℃, preferred 80～120 ℃ heating plate dry 0.5～30 minute, preferred 1～5 minute method.

The burning till preferably of substrate that is coated with aligning agent for liquid crystal carried out under 100～350 ℃ arbitrary temp, and more preferably 150～300 ℃, further more preferably 180～250 ℃.When having the acid amides acidic group in the aligning agent for liquid crystal, amic acid changes into imido conversion ratio and burns till according to this and change, but aligning agent for liquid crystal of the present invention there is no need 100% imidizate.

The thickness of filming after burning till is preferably 10～200nm, better is 50～100nm, if because blocked up, then unfavorable aspect the energy consumption of liquid crystal display cells, if thin excessively, the reliability decrease of liquid crystal display cells sometimes then.

The friction treatment that is formed at the coated surface on the substrate as stated can be used existing rubbing device.The material of friction cloth at this moment can give an example cotton, rayon, nylon etc.

The substrate of the band liquid crystal orientation film that the employing said method obtains can be made the liquid crystal structure cell through known method, make liquid crystal display cells.Make an example of liquid crystal structure cell if give an example; Then generally adopt following method: will be formed with preferred 1～30 μ m of a pair of substrate clamping of liquid crystal orientation film, the more preferably sept of 2～10 μ m; According to making frictional direction become 0～270 ° the setting of requirement at any angle; Fix with sealant on every side, seal behind the injection liquid crystal.Method to liquid crystal is enclosed does not have special qualification, can give an example injecting (ODF) method etc. of dripping that seals behind the vacuum method of liquid crystal, the liquid crystal that drips after the liquid crystal structure cell inner pressure relief that makes.

The liquid crystal display cells that gets therefrom is applicable to TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, OCB liquid crystal display cells, also has all kinds display elements such as lateral electric-field type (IPS) liquid crystal display cells, VA liquid crystal display cells.

Embodiment

Below giving an example, the present invention will be described in more detail for embodiment, but the present invention and be not interpreted as and limited by this.

(synthetic example 1)

3,5-diamido benzyl benzoate synthetic

In the four-hole boiling flask of 500mL,, drip the pyridine of 8.8g in the chlorobenzoyl chloride of 5-dinitro benzylalcohol, 14.9g, the solution of 150mL tetrahydrofuran, under room temperature, stirred 30 hours to 3 of 20.0g.After reaction finishes, add the 50mL pure water, stirred 1 hour.Add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.In organic layer, add anhydrous magnesium sulfate and dehydrate, after the filtration, desolventize with the rotary evaporator steaming.With ethyl acetate residue is carried out recrystallization, the dinitro compound of Synthetic 2 4.9g (yield 82%) with following NMR characteristic.

¹H?NMR(400MHz,CDCl ₃):δ9.03(t,1H),8.65(d,2H),8.12-8.07(m,2H),7.63(tt,1H),7.53-7.47(m,2H),5.55(s,2H)

[changing 17]

In the four-hole boiling flask of 500mL, add dinitro compound, the 2.5g of 24.9g platinum/carbon, 250g 1; 4-two

alkane stirs under room temperature under nitrogen atmosphere.Reaction is carried out diatomite filtration after finishing, and steams with rotary evaporator to desolventize.With methyl alcohol residue is carried out recrystallization, the shallow dark brown solid (yield 64%) of synthetic 12.8g.

The result who measures this shallow dark brown solid with NMR is as follows.From this results verification, the shallow dark brown solid of gained is the diamine compound as target.

¹H?NMR(400MHz,DMSO-d ₆):δ8.01-7.99(m,2H),7.69-7.64(m,1H),7.57-7.51(m,2H),5.87(d,2H),5.79(t,1H),5.06(s,2H),4.80(br,4H)

[changing 18]

(synthetic example 2)

3,5-diamido benzyl nicotinate synthetic

In the there-necked flask of 500mL, add 1 of 25.0g, the pyridine formyl chloride hydrochloride of 3-dinitro benzylalcohol, 24.6g, the N of 1.4g, the tetrahydrofuran of N-dimethyl aminopyridine, 300mL.The triethylamine of Dropwise 5 2.8mL stirred 18 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.In organic layer, add anhydrous magnesium sulfate and dehydrate, after the filtration, desolventize with the rotary evaporator steaming.Carry out recrystallization with tetrahydrofuran/hexane=1/4 pair residue, the dinitro compound with following NMR characteristic (yield 94%) of synthetic 36.0g.

¹H?NMR(400MHz,CDCl ₃):δ9.04(t,1H),8.83-8.79(m,1H),8.71-8.65(m,2H),8.19(dt,1H),7.91(d,1H),7.59-7.54(m,1H),5.64(d,2H)

[changing 19]

In the four-hole boiling flask of 500mL, add dinitro compound, the 4.5g of 29.4g platinum/carbon, 430g 1; 4-two alkane stirs under room temperature under nitrogen atmosphere.Reaction is carried out diatomite filtration after finishing, and steams with rotary evaporator to desolventize.With isopropyl alcohol residue is carried out recrystallization, the shallow dark brown solid of Synthetic 2 0.2g (yield 86%).

¹H?NMR(400MHz,CDCl ₃):δ8.80-8.76(m,1H),8.14(dt,1H),7.83(dt,1H),7.50-7.45(m,1H),6.23(d,2H),6.00(t,1H),5.28(s,2H),3.1(br,4H)

[changing 20]

(synthetic example 3)

3,5-diamido benzyl-1,3,4-trimethyl pyrazoles-5-carboxylate synthetic

In the four-hole boiling flask of 500mL, add 1,3 of 17.1g, the methylene chloride of 4-trimethyl-1H-pyrazoles-5-carboxylic acid, 250mL is cooled to temperature 0 degree.Add the oxalyl dichloro of 10.2mL, the DMF of 0.8g, under room temperature, stirred 2 hours.After the stirring, add 3 of 22.0g, the pyridine of 5-dinitro benzylalcohol, 9.7g stirred 41 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.In organic layer, add anhydrous magnesium sulfate and dehydrate, after the filtration, desolventize with the rotary evaporator steaming.Carry out the recrystallization of residue with isopropyl alcohol, obtain the dinitro compound of the following NMR characteristic of having of 18.1g.(yield 71%).

¹H?NMR(400MHz,CDCl ₃):δ9.04(t,1H),8.64(dt,2H),5.54(t,2H),4.08(s,3H),2.24(s,3H),2.21(s,3H)

[changing 21]

In the four-hole boiling flask of 500mL, add the dinitro compound of 18.0g, platinum/carbon of 1.8g, the tetrahydrofuran of 180g, under nitrogen atmosphere, stirred 17 hours.Reaction is carried out diatomite filtration after finishing, and steams with rotary evaporator to desolventize.With tetrahydrofuran and isopropyl alcohol residue is carried out recrystallization, obtain the shallow dark brown solid (yield 67%) of 9.8g.

¹H?NMR(400MHz,CDCl ₃):δ6.15(d,2H),5.98(t,1H),5.15(s,2H),4.06(s,3H),3.58(br,4H),2.18(s,6H)

[changing 22]

(synthetic example 4)

2-(pyridine-2-yl) ethyl-3,5-diaminobenzoic acid ester synthetic

In the four-hole boiling flask of 300mL, make the 2-pyridine ethanol of 23.45g, the triethylamine of 19.23g be dissolved in the tetrahydrofuran of 200ml; Be cooled to below 10 ℃, when noting heating, drip the dinitrobenzoyl chloride that makes 41.68g be dissolved in 110g tetrahydrofuran and solution.After dripping end, temperature of reaction is risen to 23 ℃, further react.After confirming that reaction finishes, reactant liquor is injected the distilled water of 1.5L, filter the solid of separating out, after the washing, disperse cleaning with the ethanol of 380g, thereby obtain the dinitro compound of the following NMR characteristic of having of 50.82g.(yield: 89%).

¹H?NMR(400MHz,DMSO-d6):δ9.76(t,1H)9.09-9.02(m,2H),8.99-8.93(m,1H),8.50(m,1H),7.64-7.60(m,1H),7.36-7.32(m,1H),4.57(s,2H),3.35(s,2H)

[changing 23]

With 1 of the dinitro compound of 48.00g, 4.8g platinum/carbon, 490g, the potpourri of 4-two

alkane under nitrogen atmosphere in 23 ℃ of stirrings.After reaction finishes, behind the diatomite filtration catalyzer, desolventize, obtain crude product with the evaporator steaming.The gained crude product disperses to clean with 300g ethanol, and the diamine compound as target that obtains having following NMR characteristic (must be measured: 27.20g, yield: 70%).

¹HNMR(400MHz,DMSO-d6):δ8.64(t,1H),8.44(d,1H),7.67(d,1H),7.34(q,1H),6.23(d,2H),5.94(s,1H),4.87(b,4H),4.39(d,2H),3.38(s,2H)

[changing 24]

Embodiment 1～10 and comparative example 1～4

Put down in writing the manufacturing example of aligning agent for liquid crystal in following embodiment 1～10 and the comparative example 1～4; The explanation of used abbreviation is described below in polyamic acid and polyimide synthetic; In addition, the method for < mensuration of molecular weight >, < mensuration of imidizate rate >, < evaluation of rub resistance >, < making of liquid crystal structure cell >, < evaluation of tilt angle >, < assay method of voltage retention>and < evaluation of savings electric charge (RDC)>is described below.

The rerum natura of each aligning agent for liquid crystal of these embodiment and comparative example (characteristic) gathers and is shown in below table 1 and table 2.

< tetracarboxylic dianhydride >

CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride

< diamines >

DABPh:3,5-diamido benzyl benzoate

DABPy:3,5-diamido benzyl nicotinate

DABTMPz:3,5-diamido benzyl-1,3,4-trimethyl-1H-pyrazoles-5-carboxylate

RefDA:2-(pyridine-2-yl) ethyl-3,5-diaminobenzoic acid ester

C14DAB:4-tetradecyloxyaniline-1, the 3-diaminobenzene

The 3-ABA:3-amino-benzylamine

< organic solvent >

The NMP:N-N-methyl-2-2-pyrrolidone N-

γ BL: gamma-butyrolacton

BC: butyl cellosolve

DPM: dipropylene glycol monomethyl ether

< mensuration of molecular weight >

The molecular weight of polyamic acid and polyimide is to measure this polyimide through following GPC (normal temperature gel permeation chromatography) device, calculates number-average molecular weight and weight-average molecular weight respectively as polyglycol and polyethylene oxide scaled value.

GPC device: Showa Denko K. K (Shodex society) system (GPC-101)

Post: Showa Denko K. K's system (series connection of KD803, KD805)

Column temperature: 50 ℃

Eluent: N, and dinethylformamide (as adjuvant, lithium bromide monohydrate (LiBrH ₂O) be that 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) are 10ml/L for 30mmol/L, tetrahydrofuran (THF))

Flow velocity: 1.0ml/ minute

Calibration curve is made and is used standard specimen: eastern ソー society of the public department of eastern Cao) system TSK standard PEO (number-average molecular weight about 900000,150000,100000,30000) and polymer laboratory company (Port リマーラボラトリー society) system polyethylene glycol (weight average molecular weight about 12000,4000,1000).

< mensuration of imidizate rate >

The imidizate rate of polyimide is calculated as follows: this polyimide is dissolved in d6-DMSO, and (dimethyl sulfoxide-d6) is measured 1H-NMR, tries to achieve imidizate not and the ratio of remaining acid amides acidic group by the ratio of the integrated value of proton peak, thereby calculates the imidizate rate.

< evaluation of rub resistance >

Each aligning agent for liquid crystal is coated on the glass substrate of band transparency electrode with spin-coating method, after on 80 ℃ the hot plate dry 5 minutes, on 210 ℃ hot plate, carries out 10 minutes burn till, formed filming of thickness 70nm.A roll diameter of 120mm friction means (Iinuma Instrument Seisakusho (Iinuma ge ー di Seisakusho) system RS01-2 type) at the roller speed 1000rpm, roller traveling speed of 50mm / s, the pressure into the volume of 0.5mm conditions using rayon cloth to the rubbing the coated surface, to obtain a substrate with a liquid crystal alignment film.With confocal laser microscopic examination liquid crystal orientation film surface.Evaluation is according to following canonical representation.

Zero: do not observe that abrasive dust adheres to and the scar that rubs.

△: observe that abrasive dust adheres to and the scar that rubs.

*: the friction scar is peeled off or be observed visually to film.

< making of liquid crystal structure cell >

Use each aligning agent for liquid crystal to be described below and make the liquid crystal structure cell.

Aligning agent for liquid crystal is coated on the glass substrate of band transparency electrode with spin-coating method, after on 80 ℃ the hot plate dry 5 minutes, on 210 ℃ hot plate, carries out 10 minutes burn till, formed filming of thickness 70nm.With Artificial Fibers cloth this coated surface is rubbed under the condition of roller rotating speed 1000rpm, roller gait of march 50mm/ second, the amount of being pressed into 0.3mm with the rubbing device of roller footpath 120mm, obtain substrate with liquid crystal orientation film.Prepare the substrate of 2 band liquid crystal orientation films; Scatter the sept of 6 μ m therein on the liquid crystal aligning face of a slice, printing and sealing agent above that then is after fitting another plate base relatively and under the condition of frictional direction quadrature the liquid crystal aligning face; Make sealant cures, made the negative crystal born of the same parents.Adopt the decompression injection method, in this negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck Japanese firm (メ Le Network ジヤパ Application society) system),, made the twisted nematic liquid crystals structure cell the inlet sealing.

< mensuration of tilt angle >

The twisted nematic liquid crystals structure cell that to use the method described in above-mentioned < making of liquid crystal structure cell>to make after 5 minutes, carries out the mensuration of tilt angle and the mensuration of voltage retention in 105 ℃ of heating.Tilt angle adopts crystal rotation method (Crystal rotation method) to measure.

< mensuration of voltage retention >

For the twisted nematic liquid crystals structure cell made from the method described in above-mentioned < making of liquid crystal structure cell >, under 90 ℃ temperature, apply the voltage 60 μ s of 4V, measure the voltage behind the 16.67ms, obtaining voltage can keep what, with this as voltage retention.Furthermore, the voltage holding ratio was measured by the voltage holding measuring apparatus (Turk nicardipine Dongyang Ltd. (black ni Te grades Dongyang Co.) system, VHR-1).

< evaluation of savings electric charge (RDC) >

Twisted nematic liquid crystals structure cell for making with the method described in above-mentioned < making of liquid crystal structure cell>applies DC voltage under 23 ℃ temperature, from OV to 1.0V, measure the flicker amplitude level under each voltage with the interval of 0.1V, processes calibration curve.Then, ground connection applied alternating voltage 3.0V, DC voltage 5.0V after 5 minutes, measured the flicker amplitude level after 1 hour, estimated RDC through contrasting ready-made calibration curve.The evaluation method of this RDC is called the flicker reference entry.

(embodiment 1)

As tetracarboxylic dianhydride's composition, as two amine components, reaction 16 hours under room temperature in the NMP of 45.18g obtains the polyamic acid solution (PAA-1) of 20 quality % with the DABPh of 6.30g (26mmol) with the CBDA of 5.00g (25mmol).

With the BC dilution of this polyamic acid solution of 10.0g (PAA-1), obtain the aligning agent for liquid crystal that the solution by the BC of the NMP of the solid constituent that contains 6 quality %, 64 quality % and 30 quality % constitutes with the NMP of 13.3g and 10.0g.

(embodiment 2)

The NMP that adds 93.33g among the polyamic acid solution that in embodiment 1, obtains (PAA-1 concentration the is 20 quality %) 40g dilutes, and adds the acetic anhydride of 5.64g and the pyridine of 2.33g again, carries out imidizate in 3 hours in 40 ℃ of reactions.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-1).The number-average molecular weight of this polyimide is 14630, and weight-average molecular weight is 32160, and the imidizate rate is 82%.

In polyimide (SPI-1) 2.00g of gained, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL, the BC of 6.00g and the DPM of 6.00g that in this solution, add 8.0g again; Stirred 20 hours in 50 ℃, obtain the aligning agent for liquid crystal that the solution by the BC of the DPM of γ-BL of the polyimide that contains 5 quality % (SPI-1), 65 quality %, 15 quality % and 15 quality % constitutes.

(embodiment 3)

As tetracarboxylic dianhydride's composition, as two amine components, reaction 16 hours under room temperature in the NMP of 45.29g obtains the polyamic acid solution (PAA-2) of 20 quality % with the DABPy of 6.32g (26mmol) with the CBDA of 5.00g (25mmol).

With the BC dilution of 10.0g polyamic acid solution (PAA-2), obtain the aligning agent for liquid crystal that the solution by the BC of the NMP of the solid constituent that contains 6 quality %, 64 quality % and 30 quality % constitutes with the NMP of 13.3g and 10.0g.

(embodiment 4)

The NMP that adds 93.33g among the polyamic acid solution that in embodiment 3, obtains (PAA-2 concentration the is 20 quality %) 40g dilutes, and adds the acetic anhydride of 5.77g and the pyridine of 2.39g again, carries out imidizate in 3 hours in 40 ℃ of reactions.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-2).The number-average molecular weight of this polyimide is 13204, and weight-average molecular weight is 30700.In addition, the imidizate rate is 87%.

In polyimide (SPI-2) 2.00g of gained, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL, the BC of 6.00g and the DPM of 6.00g that in this solution, add 8.0g again; Stirred 20 hours in 50 ℃, obtain the aligning agent for liquid crystal that the solution by the BC of the DPM of γ-BL of the polyimide that contains 5 quality % (SPI-2), 65 quality %, 15 quality % and 15 quality % constitutes.

(embodiment 5)

With the CBDA of 5.30g (27mmol) as tetracarboxylic dianhydride's composition; With the C14DAB of the 3-ABA of the DABPh of 2.00g (8mmol), 1.35g (11mmol) and 2.65g (8mmol) as two amine components; In the NMP of 45.25g, under room temperature, reacted 16 hours, obtain the polyamic acid solution (PAA-3) of 20 quality %.

With the BC dilution of 10.0g polyamic acid solution (PAA-3), obtain the aligning agent for liquid crystal that the solution by the BC of the NMP of the solid constituent that contains 6 quality %, 64 quality % and 30 quality % constitutes with the NMP of 13.3g and 10.0g.

(embodiment 6)

The NMP that adds 93.33g among the polyamic acid solution that in embodiment 5, obtains (PAA-3 concentration the is 20 quality %) 40g dilutes, and adds the acetic anhydride of 5.97g and the pyridine of 2.47g again, carries out imidizate in 3 hours in 60 ℃ of reactions.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the off-white powder of polyimide (SPI-3).The number-average molecular weight of this polyimide is 14785, and weight-average molecular weight is 37483.In addition, the imidizate rate is 88%.

In the polyimide (SPI-3) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL, the BC of 6.00g and the DPM of 6.00g that in this solution, add 8.0g again; Stirred 20 hours in 50 ℃, obtain the aligning agent for liquid crystal that the solution by the BC of the DPM of γ-BL of the polyimide that contains 5 quality % (SPI-3), 65 quality %, 15 quality % and 15 quality % constitutes.

(embodiment 7)

With the CBDA of 5.27g (27mmol) as tetracarboxylic dianhydride's composition; With the C14DAB of the 3-ABA of the DABPy of 2.00g (8mmol), 1.34g (11mmol) and 2.63g (8mmol) as two amine components; In the NMP of 44.96g, under room temperature, reacted 16 hours, obtain the polyamic acid solution (PAA-4) of 20 quality %.

With the BC dilution of 10.0g polyamic acid solution (PAA-4), obtain the aligning agent for liquid crystal that the solution by the BC of the NMP of the solid constituent that contains 6 quality %, 64 quality % and 30 quality % constitutes with the NMP of 13.3g and 10.0g.

(embodiment 8)

The NMP that adds 93.33g among the polyamic acid solution that in embodiment 7, obtains (PAA-4 concentration the is 20 quality %) 40g dilutes, and adds the acetic anhydride of 5.97g and the pyridine of 2.47g again, carries out imidizate in 3 hours in 60 ℃ of reactions.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the off-white powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 15594, and weight-average molecular weight is 42320.In addition, the imidizate rate is 87%.

In the polyimide (SPI-4) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL, the BC of 6.00g and the DPM of 6.00g that in this solution, add 8.0g again; Stirred 20 hours in 50 ℃, obtain the aligning agent for liquid crystal that the solution by the BC of the DPM of γ-BL of the polyimide that contains 5 quality % (SPI-4), 65 quality %, 15 quality % and 15 quality % constitutes.

(embodiment 9)

With the CBDA of 5.57g (29mmol) as tetracarboxylic dianhydride's composition; With the C14DAB of the 3-ABA of the DABTMPz of 2.38g (9mmol), 1.42g (12mmol) and 2.79g (9mmol) as two amine components; In the NMP of 46.7g, under room temperature, reacted 16 hours, obtain the solution of the concentration 20 quality % of polyamic acid (PAA-5).

With of the BC dilution of this polyamic acid of 10.0g (PAA-5) solution, obtain the aligning agent for liquid crystal that the solution by the BC of the NMP of the polyamic acid that contains 6 quality % (PAA-5), 64 quality % and 30 quality % constitutes with the NMP of 13.3g and 10.0g.

(embodiment 10)

The NMP that in polyamic acid (PAA-5) solution (PAA-5 concentration is 20 quality %) of the 40.0g that likewise obtains with embodiment 9, adds 93.3g dilutes, and adds the acetic anhydride of 6.06g and the pyridine of 2.53g again, reacts in 60 ℃ and carries out imidizate in 3 hours.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.With this solid matter of washed with methanol 2 times,, obtain the white dark brown powder of polyimide (SPI-5) more then in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 14222, and weight-average molecular weight is 33154.In addition, the imidizate rate is 88%.

In the polyimide (SPI-5) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL, the BC of 6.00g and the DPM of 6.00g that in this solution, add 8.00g again; Stirred 20 hours in 50 ℃, obtain the aligning agent for liquid crystal that the solution by the BC of the DPM of γ-BL of the polyimide that contains 5 quality % (SPI-5), 65 quality %, 15 quality % and 15 quality % constitutes.

(comparative example 1)

With the CBDA of 12.5g (64mmol) as tetracarboxylic dianhydride's composition; With the C14DAB of the 3-ABA of 5.56g (46mmol) and 6.25g (20mmol) as two amine components; In the NMP of 97.20g, under room temperature, reacted 16 hours, obtain the polyamic acid solution (PAA-6) of 20 quality %.

With the BC dilution of 10.0g polyamic acid (PAA-6), obtain the aligning agent for liquid crystal that the solution by the BC of the NMP of the solid constituent that contains 6 quality %, 64 quality % and 30 quality % constitutes with the NMP of 13.3g and 10.0g.

(comparative example 2)

The NMP that adds 116.67g among the polyamic acid solution that in comparative example 1, obtains (PAA-6) 50g dilutes, and adds 7.39g acetic anhydride and 3.15g pyridine, carries out imidizate in 3 hours in 70 ℃ of reactions, but in the reaction gelation has taken place.

In 50g polyamic acid solution (PAA-6), add 116.67g NMP once more and dilute, add 7.39g acetic anhydride and 3.15g pyridine, change the temperature of reaction of imidizate into 50 ℃ and react.

After being cooled to this reaction solution about room temperature, be fed in the 600ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-6).The number-average molecular weight of this polyimide is 16338, and weight-average molecular weight is 39865.In addition, the imidizate rate is 80%.

In the polyimide (SPI-6) of 1.00g, add γ-BL of 9g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL, the BC of 3.0g and the DPM of 3.0g that in this solution, add 4.0g again; Stirred 20 hours in 50 ℃, obtain the aligning agent for liquid crystal that the solution by the BC of the DPM of γ-BL of the polyimide that contains 5 quality %, 65 quality %, 15 quality % and 15 quality % constitutes.

(comparative example 3)

With the CBDA of 5.76g (29mmol) as tetracarboxylic dianhydride's composition; With the C14DAB of the 3-ABA of the RefDA of 2.31g (9mmol), 1.46g (12mmol) and 2.88g (9mmol) as two amine components; In the NMP of 56.84g, under room temperature, reacted 16 hours, obtain the polyamic acid solution (PAA-7) of 20 quality %.

With the BC dilution of 10.0g polyamic acid (PAA-7), obtain the aligning agent for liquid crystal that the solution by the BC of the NMP of the solid constituent that contains 6 quality %, 64 quality % and 30 quality % constitutes with the NMP of 13.3g and 10.0g.

(comparative example 4)

The NMP that adds 116.67g among the polyamic acid solution that in comparative example 3, obtains (PAA-7) 50g dilutes, and adds 7.39g acetic anhydride and 3.06g pyridine, carries out imidizate in 3 hours in 70 ℃ of reactions.

After being cooled to this reaction solution about room temperature, be fed in the 600ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the Sandy powder of polyimide (SPI-7).The number-average molecular weight of this polyimide is 18668, and weight-average molecular weight is 41256.In addition, the imidizate rate is 89%.

In the polyimide (SPI-7) of 1.00g, add γ-BL of 9g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL, the BC of 3.0g and the DPM of 3.0g that in this solution, add 4.0g again; Stirred 20 hours in 50 ℃, form the aligning agent for liquid crystal that the solution by the BC of the DPM of γ-BL of the polyimide that contains 5 quality %, 65 quality %, 15 quality % and 15 quality % constitutes.

The possibility of utilizing on the industry

Utilize aligning agent for liquid crystal of the present invention, tolerance with loss is strong, voltage retention is high and apply the liquid crystal orientation film that DC voltage also is difficult for taking place initial electric charge savings even can obtain the film in when friction peeled off.Therefore; The liquid crystal display cells that uses aligning agent for liquid crystal of the present invention to make can be used as the high liquid crystal display device of reliability, is suitable for various types of display elements such as TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, VA liquid crystal display cells, IPS liquid crystal display cells, OCB liquid crystal display cells.

[table 1]

[table 2]

Quote the full content of Japanese patent application 2009-283330 number instructions, claims and the specification digest of filing an application on Dec 14th, 2009 here, as the announcement of instructions of the present invention.

Claims

1. aligning agent for liquid crystal; It is characterized in that; Contain be selected from polyamic acid and with this polyamic acid imidizate and at least a polymkeric substance of polyimide, said polyamic acid reacts with tetracarboxylic dianhydride's composition through two amine components that make the diamine compound that contains following formula [1] expression and gets

[changing 1]

2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the Ar of formula [1] is the heterocyclic aromatic compound of nitrogen atom of homoatomic ring aromatics or the hexatomic ring of hexatomic ring.

3. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the Ar of formula [1] is the heterocyclic aromatic compound of pentacyclic nitrogen atom.

4. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the Ar of formula [1] is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine.

5. aligning agent for liquid crystal as claimed in claim 1; It is characterized in that the Ar of formula [1] is

azoles,

diazole, thiazole, thiadiazoles, pyrroles, imidazoles, pyrazoles or triazole.

6. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the diamine compound of formula [1] expression is any compound of formula [4]～[6] expression;

[changing 2]

7. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the diamine compound of formula [1] expression is the compound of formula [2] expression;

[changing 3]

8. like each described aligning agent for liquid crystal in the claim 1～7, it is characterized in that,, comprise the diamine compound of above following formula [3] expression of at least 10 moles of % as two amine components;

H ₂N-Ar’-R ₁-NH-R ₂ [3]

In the formula [3], Ar ' expression phenylene or naphthylene, R ₁The expression carbon number is 1～5 alkylidene, R ₂The expression carbon number is 1～5 alkyl.

9. like each described aligning agent for liquid crystal in the claim 1～8, it is characterized in that tetracarboxylic dianhydride's composition comprises the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure.

10. a liquid crystal orientation film is characterized in that, each described aligning agent for liquid crystal in the claim 1～9 is coated burnt till on the electroded substrate and get.

11. a liquid crystal display cells is characterized in that, has the described liquid crystal orientation film of claim 10.

12. the diamine compound of following formula [1] expression;

[changing 4]

13. diamine compound as claimed in claim 1, wherein, the Ar of formula [12] is the heterocyclic aromatic compound of nitrogen atom of homoatomic ring aromatics or the hexatomic ring of hexatomic ring.

14. diamine compound as claimed in claim 12, wherein, the Ar of formula [1] is the heterocyclic aromatic compound of pentacyclic nitrogen atom.

15. diamine compound as claimed in claim 12, wherein, the Ar of formula [1] is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine.

16. diamine compound as claimed in claim 12; Wherein, the Ar of formula [1] is azoles, two

azoles, thiazole, thiadiazoles, pyrroles, imidazoles, pyrazoles or triazole.

17. diamine compound as claimed in claim 12, wherein, the diamine compound of formula [1] expression is any compound of formula [4]～[6] expression;

[changing 5]

18. diamine compound as claimed in claim 12, wherein, the diamine compound of formula [1] expression is the compound of formula [2] expression;

[changing 6]

19. a polyamic acid maybe with this polyamic acid imidizate and polyimide, said polyamic acid gets through two amine components that contain each described diamine compound in the claim 12～18 are reacted with tetracarboxylic dianhydride's composition.